EP0032443A2 - Cross-linked polymers for contact lenses - Google Patents

Cross-linked polymers for contact lenses Download PDF

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Publication number
EP0032443A2
EP0032443A2 EP81300095A EP81300095A EP0032443A2 EP 0032443 A2 EP0032443 A2 EP 0032443A2 EP 81300095 A EP81300095 A EP 81300095A EP 81300095 A EP81300095 A EP 81300095A EP 0032443 A2 EP0032443 A2 EP 0032443A2
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EP
European Patent Office
Prior art keywords
monomer
cationic
polymer
vinyl
anionic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP81300095A
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German (de)
French (fr)
Other versions
EP0032443A3 (en
EP0032443B1 (en
Inventor
Ivor B. Atkinson
David C. Blackley
Barry C. Holdstock
John L. Knowlton
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CooperVision Inc
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CooperVision UK Ltd
CooperVision Inc
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Priority to AT81300095T priority Critical patent/ATE13642T1/en
Publication of EP0032443A2 publication Critical patent/EP0032443A2/en
Publication of EP0032443A3 publication Critical patent/EP0032443A3/en
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Publication of EP0032443B1 publication Critical patent/EP0032443B1/en
Expired legal-status Critical Current

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G02B1/043—Contact lenses

Definitions

  • the present invention relates to hydrophilic polymers having ionic cross-linkages, contact lenses formed therefrom and a process for their preparation.
  • Cross-linking of polymers is well-known in the art for providing polymers with desirable properties, in particular desirable mechanical properties such as high tensile strength.
  • Cross-linking is usually.effected by use of a covalent cross-linking agent which bridges two or more polymer chains linking them together by covalent ' bonding.
  • Cross-linking can also be effected by means of electrovalent interactions involving ionized sites in neighbouring polymer chains; cross-links induced in this way are known as ionic cross-links.
  • cross-linking is illustrated by ionomer resins which are ethylene copolymers containing pendant carboxylic acid groups and an associated bivalent metal cation and also by polyelectrolyte complexes which consist of an essentially neutralized mixture of polycations (e.g. a polyquaternary ammonium compound and a polyanion such as poly (vinyl sulfonic acid).
  • ionomer resins which are ethylene copolymers containing pendant carboxylic acid groups and an associated bivalent metal cation and also by polyelectrolyte complexes which consist of an essentially neutralized mixture of polycations (e.g. a polyquaternary ammonium compound and a polyanion such as poly (vinyl sulfonic acid).
  • Cross-linking of hydrophilic polymers for use as contact lens materials is often a practical necessity in order that the material has adequate mechanical properties in the hydrated state.
  • Covalent cross-linkage has been widely used for this purpose but ionic cross-linking has not hitherto been used.
  • Ionic cross-linking requiring the presence of a bivalent metal cation is not acceptable for contact lens material since in use the bivalent cations are largely leached from the polymer by tear fluid and replaced by sodium and potassium ions contained in the tear fluid; polyelectrolyte complexes are unsuitable since they cannot conveniently be prepared in a form suitable for machining on a lathe.
  • a novel polymer for use as a contact lens material and comprised of chains in each of which there are both cationic and anionic sites participating in electrovalent cross-linkage of the chains one to another, the aforesaid sites being provided by moieties of the polymer chains which are resistant to loss of polarity by contact with tear fluids.
  • the invention provides a contact lens which comprises a hydrophilic polymer of at least one hydrophilic vinyl or vinylidene monomer, a minor proportion of a cationic group - containing monomer and a minor proportion of an anionic group - containing monomer and said ionic group - containing monomers providing cationic and anionic sites for ionic cross-linkages between polymer chains.
  • the moieties providing the ionic sites will usually be organic moieties polymerized into the polymer chains and in general such organic moieties will be units of monomer material copolymerized into a backbone polymer.
  • the monomer material may, for example, be an alkyl amino acrylate or methacrylate, such as dimethylaminoethylmethacrylate, t-butylaminoethylmethacrylate or di-n-butylaminoethylmethacrylate, in the case of monomer material providing cationic sites.
  • methacrylic or acrylic acid may be employed to provide anionic sites although other polymerizable carboxylic acids may be used.
  • cationic and anionic moieties as quaternary ammonium compounds and unsaturated sulfonic acids may be employed to provide the cationic and anionic sites although, it should be noted, particularly in the case of relatively strongly ionizing groups, that there may be difficulties as regards availability of materials.
  • Vinyl sulfonic acid, styrene sulfonic acid and unsaturated phosphoric acid monomers are however, obtainable.
  • the polymers of the invention will normally contain the ionic moieties in a comparatively minor proportion together with a balance of polymerized essentially non-ionic monomer material.
  • the balance may, for example, be made up of polymerized hydrophilic monomer such as an hydroxy alkyl acrylate or methacrylate, e.g. 2-hydroxyethylmethacrylate or N-vinylpyrrolidone and/or a polymerized hydrophobic monomer, such as an alkyl acrylate or methacrylate or styrene or a substituted styrene.
  • Typical hydrophobic monomers are methyl methacrylate and n-butyl methacrylate.
  • Copolymers of 2-hydroxyethylmethacrylate with dimethylaminoethylmethacrylate, methacrylic acid and optionally styrene have been found to be especially suitable for use as soft contact lens material.
  • the anionic moieties may be present in substantially stoichiometrically equivalent amounts, but, if desired, one ionic moiety may be in stoichiometric excess.
  • a stoichiometric excess of the anionic moiety provides a powerful hydration mechanism in the alkaline environment of the eye so that in most instances such an excess will be considered desirable.
  • the ionic groups are in excess they are preferably neutralised by treatment of the final polymer with a mildly alkaline solution as described in British Patent No. 1,548,158 (the disclosure of which is specifically incorporated herein by reference).
  • the ionic moieties will in general be present in relatively minor proportions.
  • the proportion of ionic moieties available for participation in electrovalent linkage will be in the range from about 5% to about 20% by weight, preferably 7% to 20% (e.g. from about 7% to 17% by weight). In all cases, the percentages stated are by weight of the whole unhydrated polymer.
  • Polymers according to the invention can conveniently be made by polymerizing a monomer mixture comprising components of identity and content appropriate to the desired polymer, the polymerization being effected using, for example, azobisisobutyronitrile as initiator.
  • Other initiators may alternatively be employed although peroxide initiators are not at present recommended since they have been found to produce dark coloured polymers.
  • the polymers of the invention have been found, as will be appreciated from the Examples which follow, to exhibit good mechanical properties. This is thought to be a result of the labile character of the electrovalent cross-linkage forces which results in the polymeric material being able to yield locally to applied stress.
  • the polymers of the invention may, in addition to cross-linkages as a result of electrovalency, contain covalent cross-linkages as a result of use, if desired, of a covalent cross-linking agent, and results in polymers having even better mechanical properties.
  • Covalent cross-linkages may be incorporated in the polymers by including a di- or poly functional cross-linking agent, such as glycol dimethacrylates or acrylates, allyl methacrylate or acrylate or triallyl cyanurate.
  • the polymer of the invention can readily be cast to form a lens or lens blank.
  • Lens blanks can be machined in known manner to form contact lenses of desired configuration.
  • I Lenses made in this way from hydrophilic monomer-derived polymers can be hydrated to equilibrium after machining using saline solution as described, for example, in British Patent No. 1,548,158.
  • the invention includes within its scope lenses, blanks and machined lenses as just described and in particular includes such lenses and lens blanks made of.polymer comprising the following polymerized monomer units in the following proportions by weight:-
  • Polymers were prepared according to the formulations given in Table 1. 2-hydroxyethylmethacrylate (2-HEMA) with a very low (0.05 wt%) ethylene glycol dimethacrylate (EGDM) content was used and hence the polymer was expected to contain a very low concentration of derived covalent cross-links.
  • the monomer mixtures were polymerized by thoroughly mixing together purified.2-HEMA, redistilled MA, DMAEMA and (where stated styrene) in the proportions stated in Table 1 using the stated quantity of azodiisobutyronitrile (AZDN) as free radical generator. Polymerization was carried out in polythene tubes at 65 0 C for 16 hours, followed by curing for 3 hours at 100°C. In the case of comparison Examples 1 and 3, the DMAEMA was omitted, as indicated.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Eyeglasses (AREA)

Abstract

Contact lenses are disclosed which are formed from hydrophilic polymers of at least one hydrophilic monomer and minor proportions of at least one monomer containing cationic groups and at least one monomer containing anionic groups so that ionic cross-linkages can form between polymer molecules. Typical monomers containing cationic groups are alkyl amino acrylates and methacrylates and typical monomers containing anionic groups are methacrylic and acrylic acids and such monomers may be employed in proportions by weight of from about 5% to about 20%. Suitable hydrophilic monomers include hydroxy alkyl acrylates and methacrylates.

Description

  • The present invention relates to hydrophilic polymers having ionic cross-linkages, contact lenses formed therefrom and a process for their preparation.
    • BACKGROUND OF THE INVENTION
  • Cross-linking of polymers is well-known in the art for providing polymers with desirable properties, in particular desirable mechanical properties such as high tensile strength. Cross-linking is usually.effected by use of a covalent cross-linking agent which bridges two or more polymer chains linking them together by covalent 'bonding. Cross-linking can also be effected by means of electrovalent interactions involving ionized sites in neighbouring polymer chains; cross-links induced in this way are known as ionic cross-links. This form of cross-linking is illustrated by ionomer resins which are ethylene copolymers containing pendant carboxylic acid groups and an associated bivalent metal cation and also by polyelectrolyte complexes which consist of an essentially neutralized mixture of polycations (e.g. a polyquaternary ammonium compound and a polyanion such as poly (vinyl sulfonic acid).
  • Cross-linking of hydrophilic polymers for use as contact lens materials is often a practical necessity in order that the material has adequate mechanical properties in the hydrated state. Covalent cross-linkage has been widely used for this purpose but ionic cross-linking has not hitherto been used. Ionic cross-linking requiring the presence of a bivalent metal cation is not acceptable for contact lens material since in use the bivalent cations are largely leached from the polymer by tear fluid and replaced by sodium and potassium ions contained in the tear fluid; polyelectrolyte complexes are unsuitable since they cannot conveniently be prepared in a form suitable for machining on a lathe.
    • BRIEF DESCRIPTION OF THE INVENTION
  • According to one aspect of the invention, there is provided a novel polymer for use as a contact lens material and comprised of chains in each of which there are both cationic and anionic sites participating in electrovalent cross-linkage of the chains one to another, the aforesaid sites being provided by moieties of the polymer chains which are resistant to loss of polarity by contact with tear fluids.
  • In a more specific embodiment the invention provides a contact lens which comprises a hydrophilic polymer of at least one hydrophilic vinyl or vinylidene monomer, a minor proportion of a cationic group - containing monomer and a minor proportion of an anionic group - containing monomer and said ionic group - containing monomers providing cationic and anionic sites for ionic cross-linkages between polymer chains.
  • The moieties providing the ionic sites will usually be organic moieties polymerized into the polymer chains and in general such organic moieties will be units of monomer material copolymerized into a backbone polymer. The monomer material may, for example, be an alkyl amino acrylate or methacrylate, such as dimethylaminoethylmethacrylate, t-butylaminoethylmethacrylate or di-n-butylaminoethylmethacrylate, in the case of monomer material providing cationic sites. Conveniently methacrylic or acrylic acid may be employed to provide anionic sites although other polymerizable carboxylic acids may be used. Alternatively, however, such other cationic and anionic moieties as quaternary ammonium compounds and unsaturated sulfonic acids may be employed to provide the cationic and anionic sites although, it should be noted, particularly in the case of relatively strongly ionizing groups, that there may be difficulties as regards availability of materials. Vinyl sulfonic acid, styrene sulfonic acid and unsaturated phosphoric acid monomers are however, obtainable.
  • " The polymers of the invention will normally contain the ionic moieties in a comparatively minor proportion together with a balance of polymerized essentially non-ionic monomer material. The balance may, for example, be made up of polymerized hydrophilic monomer such as an hydroxy alkyl acrylate or methacrylate, e.g. 2-hydroxyethylmethacrylate or N-vinylpyrrolidone and/or a polymerized hydrophobic monomer, such as an alkyl acrylate or methacrylate or styrene or a substituted styrene. Typical hydrophobic monomers are methyl methacrylate and n-butyl methacrylate.
  • Copolymers of 2-hydroxyethylmethacrylate with dimethylaminoethylmethacrylate, methacrylic acid and optionally styrene have been found to be especially suitable for use as soft contact lens material.
  • The anionic moieties may be present in substantially stoichiometrically equivalent amounts, but, if desired, one ionic moiety may be in stoichiometric excess. For example, a stoichiometric excess of the anionic moiety provides a powerful hydration mechanism in the alkaline environment of the eye so that in most instances such an excess will be considered desirable. In such cases, where the ionic groups are in excess they are preferably neutralised by treatment of the final polymer with a mildly alkaline solution as described in British Patent No. 1,548,158 (the disclosure of which is specifically incorporated herein by reference).
  • As indicated earlier, the ionic moieties will in general be present in relatively minor proportions. Generally the proportion of ionic moieties available for participation in electrovalent linkage will be in the range from about 5% to about 20% by weight, preferably 7% to 20% (e.g. from about 7% to 17% by weight). In all cases, the percentages stated are by weight of the whole unhydrated polymer.
  • Polymers according to the invention can conveniently be made by polymerizing a monomer mixture comprising components of identity and content appropriate to the desired polymer, the polymerization being effected using, for example, azobisisobutyronitrile as initiator. Other initiators may alternatively be employed although peroxide initiators are not at present recommended since they have been found to produce dark coloured polymers.
  • The polymers of the invention have been found, as will be appreciated from the Examples which follow, to exhibit good mechanical properties. This is thought to be a result of the labile character of the electrovalent cross-linkage forces which results in the polymeric material being able to yield locally to applied stress. The polymers of the invention may, in addition to cross-linkages as a result of electrovalency, contain covalent cross-linkages as a result of use, if desired, of a covalent cross-linking agent, and results in polymers having even better mechanical properties. Covalent cross-linkages may be incorporated in the polymers by including a di- or poly functional cross-linking agent, such as glycol dimethacrylates or acrylates, allyl methacrylate or acrylate or triallyl cyanurate.
  • The polymer of the invention can readily be cast to form a lens or lens blank. Lens blanks can be machined in known manner to form contact lenses of desired configuration. I Lenses made in this way from hydrophilic monomer-derived polymers can be hydrated to equilibrium after machining using saline solution as described, for example, in British Patent No. 1,548,158.
  • The invention includes within its scope lenses, blanks and machined lenses as just described and in particular includes such lenses and lens blanks made of.polymer comprising the following polymerized monomer units in the following proportions by weight:-
    Figure imgb0001
  • The following specific Examples are intended to illustrate the invention.
    • Examples 1 to 5
  • Polymers were prepared according to the formulations given in Table 1. 2-hydroxyethylmethacrylate (2-HEMA) with a very low (0.05 wt%) ethylene glycol dimethacrylate (EGDM) content was used and hence the polymer was expected to contain a very low concentration of derived covalent cross-links. The monomer mixtures were polymerized by thoroughly mixing together purified.2-HEMA, redistilled MA, DMAEMA and (where stated styrene) in the proportions stated in Table 1 using the stated quantity of azodiisobutyronitrile (AZDN) as free radical generator. Polymerization was carried out in polythene tubes at 650C for 16 hours, followed by curing for 3 hours at 100°C. In the case of comparison Examples 1 and 3, the DMAEMA was omitted, as indicated.
  • The rods obtained were cut into lens blanks, machined to form lenses, extracted and hydrated to equilibrium in a saline solution buffered at pH7.4. The properties were then determined and the results are presented in Table 2. It can be seen that polymers of high tensile strength, as judged by the burst test, can be prepared even in the apparent absence of covalent cross-links.
  • This observation and the fact that the water content of the gels containing DMAEMA are somewhat lower than those without, in spite of the hydrophilic nature of DMAEMA and twice the addition of methacrylic acid, provides convincing evidence that hydrogels which contain minor proportions of cationic and anionic sites contain physically- effective cross-links attributable to the simultaneous presence of both types of ionic-site.
    Figure imgb0002
    Figure imgb0003

Claims (12)

1. A polymeric contact lens formed by addition polymerization of at least one hydrophilic, ethylenically-unsaturated monomer, an ethylenically-unsaturated monomer containing a cationic group and an ethylenically-unsaturated monomer containing an anionic group, said cationic and anionic groups forming ionic cross-linkages whereby the lens exhibits improved burst strength as compared with a similar lens containing no ionic cross-linkages.
2. A contact lens according to claim 1 wherein the monomer containing a cationic group is a vinyl or vinylidene monomer having an amino group or quaternary ammonium group.
3. A contact lens according to claim 2 wherein the vinyl or vinylidene monomer is an alkyl amino acrylate or methacrylate.
4. A contact lens according to any one of the preceding claims wherein the monomer containing an anionic group is a vinyl or vinylidene monomer having a carboxylic or sulfonic acid group.
5. A contact lens which comprises a polymer of a hydrophilic vinyl or vinylidene monomer containing a single center of unsaturation, a cationic vinyl or vinylidene monomer having alkyl amino or quaternary ammonium cationic groups and an anionic vinyl or vinylidene monomer having carboxylic or sulfonic acid anionic groups, said cationic and anionic groups constituting pendant or terminal groups in the polymer which interact to form ionic cross-linkages.
6. A contact lens according to claim 5 wherein the anionic monomer is present in the polymer in stoichiometric excess with respect to the cationic monomer.
7. A contact lens according to claim 5 or claim 6 wherein the cationic and anionic monomers are present in the polymer in a total amount of from about 5 to about 20% by weight.
8. A contact lens according to any one of claims 5 to 7 wherein the polymer also contains covalent cross-linkages derived from cross-linking monomers containing at least two centers of unsaturation.
9. A contact lens according to any one of claims 5 to 8 wherein the polymer is an addition polymer of at least one hydrophilic monomer and at least one hydrophobic monomer.
10. A contact lens which comprises a polymeric hydrogel which is the hydrated polymerized product of a monomer mixture comprising a minor proportion by weight of vinyl or vinylidene monomers containing cationic and anionic groups and a major proportion of polymerizable monomer having a single center of unsaturation, said monomer mixture including sufficient hydrophilic monomer to render the resultant polymer hydrophilic and the monomers containing cationic and anionic groups being effective in forming ionic cross-linkages in the resultant polymer.
11. A hydrophilic polymer which comprises an addition polymer of at least one hydrophilic vinyl or vinylidene monomer, a minor proportion by weight of a copolymerizable monomer containing anionic groups and a minor proportion by weight of a copolymerizable monomer containing cationic groups, the anionic and cationic groups forming ionic cross-linkages.
12. A method of preparing a hydrophilic copolymer containing ionic cross-linkages which comprises subjecting to polymerization in the presence of a free-radical initiator a monomer mixture comprising at least one hydrophilic vinyl or vinylidene monomer containing a single center of unsaturation, a vinyl or vinylidene monomer containing a cationic group and a vinyl or vinylidene monomer containing anionic groups.
EP81300095A 1980-01-10 1981-01-09 Cross-linked polymers for contact lenses Expired EP0032443B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT81300095T ATE13642T1 (en) 1980-01-10 1981-01-09 CROSSLINKED POLYMERS FOR CONTACT LENSES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8000809 1980-01-10
GB8000809 1980-01-10

Publications (3)

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EP0032443A2 true EP0032443A2 (en) 1981-07-22
EP0032443A3 EP0032443A3 (en) 1981-10-14
EP0032443B1 EP0032443B1 (en) 1985-06-05

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AT (1) ATE13642T1 (en)
DE (1) DE3170785D1 (en)
GB (1) GB2068980A (en)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992007885A1 (en) * 1990-10-29 1992-05-14 Biocompatibles Limited Contact lens material
EP0563299A1 (en) * 1990-12-21 1993-10-06 Hydron Limited Balanced charge polymer and hydrophilic contact lens manufactured therefrom
EP0766552A1 (en) * 1994-06-21 1997-04-09 Ppg Industries, Inc. Hair fixative amphoteric polymer composition
US6451871B1 (en) 1998-11-25 2002-09-17 Novartis Ag Methods of modifying surface characteristics
US6719929B2 (en) 2000-02-04 2004-04-13 Novartis Ag Method for modifying a surface
US6793973B2 (en) 2000-02-04 2004-09-21 Novartis Ag Single-dip process for achieving a layer-by-layer-like coating
US6827966B2 (en) 2001-05-30 2004-12-07 Novartis Ag Diffusion-controllable coatings on medical device
US6852353B2 (en) 2000-08-24 2005-02-08 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
US6858248B2 (en) 2001-05-30 2005-02-22 Novartis Ag Method for applying a coating to a medical device
US6893685B2 (en) 2000-08-24 2005-05-17 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
US6896926B2 (en) 2002-09-11 2005-05-24 Novartis Ag Method for applying an LbL coating onto a medical device
US6926965B2 (en) 2002-09-11 2005-08-09 Novartis Ag LbL-coated medical device and method for making the same
WO2007088392A1 (en) * 2006-02-03 2007-08-09 The Queen's University Of Belfast Material and uses thereof
US7811601B2 (en) * 2003-04-03 2010-10-12 Seed Co., Ltd. Ophthalmic lenses capable of sustained drug release and preservative solutions therefor
US8044112B2 (en) 2006-03-30 2011-10-25 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
US8158192B2 (en) 2006-12-21 2012-04-17 Novartis Ag Process for the coating of biomedical articles
US8460743B2 (en) 2008-03-18 2013-06-11 Novartis Ag Coating process for ophthalmic lenses
US9005700B2 (en) 2011-10-12 2015-04-14 Novartis Ag Method for making UV-absorbing ophthalmic lenses
US9052442B2 (en) 2006-10-30 2015-06-09 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
US10338408B2 (en) 2012-12-17 2019-07-02 Novartis Ag Method for making improved UV-absorbing ophthalmic lenses

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CS257979B1 (en) * 1986-06-24 1988-07-15 Otto Wichterle Hydrophilic copolymer and method of its production
GB0620537D0 (en) * 2006-10-17 2006-11-22 Univ Southampton Copolymers suitable for use in corneal bandages

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634366A (en) * 1968-05-23 1972-01-11 Daicel Ltd Polymerizing method
US3926756A (en) * 1968-12-06 1975-12-16 Hercules Inc Process for preparing high molecular-weight, water soluble vinyl polymers by irradiation
US4041020A (en) * 1974-08-05 1977-08-09 The Dow Chemical Company Process for spinning absorbent articles from copolymers having a copolymerized crosslinker
US4071650A (en) * 1974-08-05 1978-01-31 The Dow Chemical Company Films and absorbent articles made from copolymers having a copolymerized crosslinker
GB1548158A (en) * 1976-03-19 1979-07-04 Global Vision Uk Ltd Contact lens having high oxygen permeability
US4172177A (en) * 1975-06-17 1979-10-23 Kyowa Gas Chemical Industry Co., Ltd. Water insoluble hydrophilic polymer composition
US4212782A (en) * 1978-05-08 1980-07-15 Normac, Inc. Polymers of acid addition salts of methacrylic acid and a 2-mono(lower)alkylaminoethyl methacrylate
US4218554A (en) * 1978-10-11 1980-08-19 Foley William M Jr Process for preparing hydrogel contact lenses containing quaternary ammonium salts

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634366A (en) * 1968-05-23 1972-01-11 Daicel Ltd Polymerizing method
US3926756A (en) * 1968-12-06 1975-12-16 Hercules Inc Process for preparing high molecular-weight, water soluble vinyl polymers by irradiation
US4041020A (en) * 1974-08-05 1977-08-09 The Dow Chemical Company Process for spinning absorbent articles from copolymers having a copolymerized crosslinker
US4071650A (en) * 1974-08-05 1978-01-31 The Dow Chemical Company Films and absorbent articles made from copolymers having a copolymerized crosslinker
US4172177A (en) * 1975-06-17 1979-10-23 Kyowa Gas Chemical Industry Co., Ltd. Water insoluble hydrophilic polymer composition
GB1548158A (en) * 1976-03-19 1979-07-04 Global Vision Uk Ltd Contact lens having high oxygen permeability
US4212782A (en) * 1978-05-08 1980-07-15 Normac, Inc. Polymers of acid addition salts of methacrylic acid and a 2-mono(lower)alkylaminoethyl methacrylate
US4218554A (en) * 1978-10-11 1980-08-19 Foley William M Jr Process for preparing hydrogel contact lenses containing quaternary ammonium salts

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6420453B1 (en) 1990-10-29 2002-07-16 Biocompatibles Limited Contact lens material
US6423761B1 (en) 1990-10-29 2002-07-23 Biocompatibles Limited Contact lens material
WO1992007885A1 (en) * 1990-10-29 1992-05-14 Biocompatibles Limited Contact lens material
EP0563299A1 (en) * 1990-12-21 1993-10-06 Hydron Limited Balanced charge polymer and hydrophilic contact lens manufactured therefrom
EP0563299A4 (en) * 1990-12-21 1994-07-20 Ceskoslovenska Akademie Ved Balanced charge polymer and hydrophilic contact lens manufactured therefrom
EP0751404A2 (en) * 1990-12-21 1997-01-02 Hydron Limited Balanced charge polymer and hydrophilic contact lens manufactured therefrom
EP0751404A3 (en) * 1990-12-21 1997-10-01 Hydron Ltd Balanced charge polymer and hydrophilic contact lens manufactured therefrom
EP0766552A4 (en) * 1994-06-21 1999-08-25 Ppg Industries Inc Hair fixative amphoteric polymer composition
EP0766552A1 (en) * 1994-06-21 1997-04-09 Ppg Industries, Inc. Hair fixative amphoteric polymer composition
US7875660B2 (en) 1998-01-09 2011-01-25 Novartis Ag Biomedical devices having improved surface characteristics
US7705067B2 (en) 1998-01-09 2010-04-27 Novartis Ag Biomedical device having improved surface characteristics
US7566746B2 (en) 1998-01-09 2009-07-28 Novartis Ag Biomedical devices having improved surface characteristics
US7297725B2 (en) 1998-01-09 2007-11-20 Novartis Ag Biomedical devices having improved surface characteristics
US6451871B1 (en) 1998-11-25 2002-09-17 Novartis Ag Methods of modifying surface characteristics
US7022379B2 (en) 2000-02-04 2006-04-04 Novartis Ag Single-dip process for achieving a layer-by-layer-like coating
US6719929B2 (en) 2000-02-04 2004-04-13 Novartis Ag Method for modifying a surface
US6793973B2 (en) 2000-02-04 2004-09-21 Novartis Ag Single-dip process for achieving a layer-by-layer-like coating
US7040756B2 (en) 2000-08-24 2006-05-09 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
US6893685B2 (en) 2000-08-24 2005-05-17 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
US6852353B2 (en) 2000-08-24 2005-02-08 Novartis Ag Process for surface modifying substrates and modified substrates resulting therefrom
US6858248B2 (en) 2001-05-30 2005-02-22 Novartis Ag Method for applying a coating to a medical device
US6827966B2 (en) 2001-05-30 2004-12-07 Novartis Ag Diffusion-controllable coatings on medical device
US7666461B2 (en) 2001-05-30 2010-02-23 Novartis Ag Diffusion-controllable coatings on medical device
US6896926B2 (en) 2002-09-11 2005-05-24 Novartis Ag Method for applying an LbL coating onto a medical device
US6926965B2 (en) 2002-09-11 2005-08-09 Novartis Ag LbL-coated medical device and method for making the same
US7582327B2 (en) 2002-09-11 2009-09-01 Novartis Ag LbL-coated medical device and method for making the same
US7811601B2 (en) * 2003-04-03 2010-10-12 Seed Co., Ltd. Ophthalmic lenses capable of sustained drug release and preservative solutions therefor
WO2007088392A1 (en) * 2006-02-03 2007-08-09 The Queen's University Of Belfast Material and uses thereof
JP2009525108A (en) * 2006-02-03 2009-07-09 ザ クイーンズ ユニバーシティ オブ ベルファスト Materials and their use
US8450359B2 (en) 2006-02-03 2013-05-28 The Queen's University Of Belfast Polymer-supported photosensitizers for the generation of singlet oxygen
US8044112B2 (en) 2006-03-30 2011-10-25 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
US9052442B2 (en) 2006-10-30 2015-06-09 Novartis Ag Method for applying a coating onto a silicone hydrogel lens
US8158192B2 (en) 2006-12-21 2012-04-17 Novartis Ag Process for the coating of biomedical articles
US8460743B2 (en) 2008-03-18 2013-06-11 Novartis Ag Coating process for ophthalmic lenses
US9005700B2 (en) 2011-10-12 2015-04-14 Novartis Ag Method for making UV-absorbing ophthalmic lenses
US10338408B2 (en) 2012-12-17 2019-07-02 Novartis Ag Method for making improved UV-absorbing ophthalmic lenses

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ATE13642T1 (en) 1985-06-15
DE3170785D1 (en) 1985-07-11
GB2068980A (en) 1981-08-19
EP0032443A3 (en) 1981-10-14
EP0032443B1 (en) 1985-06-05

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